Textile yarns impregnated with lubricating compositions



Patented Feb. 7, 1950 I 2,496,776 I TEXTILE YARNS IMPREGNATED wrrn LUBRICATING COMPOSITIONS John R. Caldwell, Kingsport, 'Ienn.,. assignor to Eastman Kodak Company. =R-ochester, N. Y.,. a corporation of New Jersey No Drawing. Original application Jun Serial No. 678,353. Divided. and this application February 1'7, 1948, Serial No. 9,023 I This invention relates to the preparation of amides of acetoacetic acid and more particularly with the preparation of amides containing the acetoacetate radical in combination with a long chain aliphatic hydrocarbon radical containing from 8 to 24 carbon atoms.

This is a division of my copending application 678,353, filed June 21, 1946, now Patent 2,462,358 of February 22, 1949.

An object of the invention is to provide a process for making a new class of acetoacetyl amide compounds containing ketone groups in combination with amide groups and long chain hydrocarbon radicals. A further object of the invention is to provide a new class of plasticizers and softeners for cellulose inorganic and organic ester plastics and for the vinyl resins. The invention further provides new and improved conditioning agents for the treatment of yarns and fabrics. Many of the compounds of the invention are oil soluble and may be added to lubricating oils and greases in order to improve the film strength and adhesion to metals. The new compounds are also valuable as surface active agents and may be employed as emulsifiers and detergents. Other objects will appear hereinafter.

In accordance with the invention these and other objects are attained by condensing acetoacetic acid or a compound in which the acetoacetyl radical is readily available with a substituted aliphatic amine or polyamine to produce compounds having the general structure R1 oHlooomom-N wherein R1 and R2 each may be a hydrocarbon radical containing 8 to 24 carbon atoms which may be interrupted by one or more nitrogen atoms in the chain, and which radical may also contain amide linkages. Either, but not both, R1 or R2 may also be a hydrogen atom when the other has the above stated values.

R1 and R2, for example, may include the hydrocarbon radicals CsI-I1'1, C'10H21--,

ience, it is preferred to employ diketene as the source of the acetoacetyl radical CH3COCH2CO-.

2 Claims. (01. LIT-139.5)

polymerization of has the structure Diketene is derived from the two molecules of ketene and CH3=CCH'2 o- -o=0 Diketene reacts with amines according to the equation:

wherein R1 and R2 have the significance described above. I

The compounds of the invention are readily prepared by reactions of the following types:

(a) Diketene is treated with a long chain alkylamine as represented by the equation:

. CHE-c OCH,-O o-Nnclnn .(b) A: fatty acid is condensed with a polyamine. to produce a mixed amino-amide compound:

This product is then treated with diketene to form the acetoacetic derivative cum-o O-NHCH4NHO 0 011,0 0 OH; Fatty acids that may be employed in the process of the invention include oleic, lauric, stearic, palmitic', ricinoleic, pelargonic, capric and arachidi'c acid. Also the naphthenic acids derived from. petroleum and containing 8 or more carbon atoms are advantageously adapted to the invention.

The diketene is reacted with the long chain alkylamine preferably in the presence of an inert diluent such as ethylene dichloride, dioxane and toluene and'so forth, to aid in controlling the rate of reaction since the reaction is a vigorous exothermic reaction. The solution is stirred and the temperature is maintained by suitable cool ing apparatus below 60 C. and preferably in most instances in the range of 45-50 C. or below. At the conclusion of the reaction the diluent is distilled from the'product.

If it is desired to form the alkylamine, the fatty acid and the amine selected may be'heated in an esterificati'on apparatus employing a suitable water entrainer such as toluene and a suitable catalyst for the reaction such as toluene sulfonic acid. The heating may be conductedat approximately C..until substantial amounts of water are formed. This solution now containing alkylamines may then be cooled within the range of 4050 CI and'dikete'ne may be added while the solution is stirred. At the conclusion of the vig- 3 oi'ou's exothermic reaction. the toluene may be evaporated 01f under vacuum and the product, and acetoacetamide, remains as the residue.

The invention is further described in the fol lowing examples:

Ewample I Oleyl amine (octadecenylamine) (265g. or 1.0

ticularly with those mentioned hereinafter and may be employed as a plasticizer for them.

The acetoacetic amide compounds of the invention are valuable plasticizers for cellulose inmol.) is dissolved in 500 cc. of ethylene dichloride. The solution is stirred and the temperature is maintained at 45-50 C. while 84 g. (1 mol.) of diketene is slowly added. A vigorous exothermic reaction takes place. The ethylene dichloride is evaporated to leave residue that is N-acetoacetyl oleyl amine, having the structure CH3COCH2COUHC18H35. The product is soluble in many organic solvents and is compatible with many types of cellulose esters and vinyl resins. It has a soft, waxy texture and is valuable as a textile treating agent. When applied to yarns and fabrics. theN-acetoacetyl oleyl amine imparts a soft, smooth hand and also acts as an anti-static agent.

Example II 103 g. of diethylene triamine and 420 g. oleic acid were heated at 120? C. in an esterification apparatus, using toluene as a water entrainer and toluene sulfonic acid as a catalyst. Heating was continued until 28 to 30 cc. of water was eliminated. The product consists primarily of a mixture of amine-amides having the structure R is derived from oleic acid. The toluene solution of the amino-amides is cooled to 40-50 C. and stirred while 126 g. (1.5 mols.) of diketene is added. The toluene is then evaporated under vacuum to leave a viscous oil. The product consists essentially of the compounds:

Stearic acid and ethylenediamine' are condensed by known methods to give the half-amide oxane and stirred at 50-60 C. While one mol of diketene is slowly added. The dioxane is evaporated in vacuum to leave a hard wax, melting at about 80-90 C. and having the structure The product is compatible with cellulose inorganic and organic acid esters and others para soft, waxy 65 One mol of the half-amide is dissolved in di-- organic and organic ester base plastics as represented by cellulose nitrate, and cellulose acetate, cellulose acetate propionate, cellulose acetate, butyrate, cellulose propionate, and cellulose propionate butyrate in which various percentages of ester roups are present. The compounds are also advantageously employed as plasticizers for cellulose ethers as represented by ethyl cellulose and benzyl cellulose, and for many types of vinyl resins including polyvinyl acetate, polyvinyl acetate-chloride etc.

The acetoacetic amide compounds containing the higher fatty acids the alkyl radicals of which have carbon atoms from 012 to C20 and particularly stearic and oleic radicals are useful as textile finishing agents. These compounds impart a soft, smooth hand to yarns and fabrics and reduce the tendency toward static electrification.

The acetoacetic amides of the invention may be added to lubricating oils and greases to imrove film strength and adhesion to metals or may be employed as emulsifiers, detergents and surface active agents.

I claim:

1. Textile yarns amenable to textile operations including weaving and spinning, impregnated with a lubricant containing as its essential lubricating and softening component an acetoacetyl amide selected from the group consisting of T and JOHN R. CALDWELL.,

REFERENCES CITED The following references are of record in the file of this patent:

I cmrsn STATES PATENTS Date Name 2,152,132 Boese Mar. 28, 1939. 2,201,041 Katz M May 14, 1940 2,243,980 Rheiner June 3, 1941 2,340,881 Kelley et a]. Feb. 8, 1944 2,345,632 Robinson Apr. 4, 1944 OTHER REFERENCES .Boese, Diketene, a New Industrial Chemical, Ind. and Eng. Chem, vol. 32, No. 1, 1940, pages 16 to 22. 

1. TEXTILE YARNS AMENABLE TO TEXTILE OPERATIONS INCLUDING WEAVING AND SPINNING, IMPREGNATED WITH A LUBRICANT CONTAINING AS ITS ESSENTIAL LUBRICATING AND SOFTENING COMPONENT AS ACETOACETYL AMIDE SELECTED FROM THE GROUP CONSISTING OF 